著者

財津 桂 片木 宗弘 中西 啓子 志摩 典明 鎌田 寛恵 鎌田 徹 西岡 裕 三木 昭宏 辰野 道昭 岩村 樹憲 佐藤 貴子 土橋 均 鈴木 廣一

出版者

日本法科学技術学会

雑誌

日本法科学技術学会誌 (ISSN:18801323)

巻号頁・発行日

vol.16, no.2, pp.73-90, 2011 (Released:2011-08-12)

参考文献数

31

被引用文献数

4 3

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Comprehensive analytical method to identify 11 kinds of synthetic cannabinoids has been investigated by thin layer chromatography (TLC), gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). The analytes used in this study have already been detected from various herbal-type designer drugs: 8 kinds of aminoalkylindoles (AAIs) (JWH-015, JWH-018, JWH-073, JWH-081, JWH-200, JWH-250, JWH-251 and JWH-398), two kinds of cyclohexylphenols (CPs) (CP 47,497 and Cannabicyclohexanol), and a Δ9-tetrahydrocannabinol analog (HU-210).   Although specific color changes were observed for the cannabinoids using Marquis reagent, identification of each analyte based on Rf values was difficult to be obtained by TLC.   On the other hand, GC/MS and LC/MS/MS were appropriate for their qualitative analyses because of their chromatographic and mass spectral differentiation. A semi-polar capillary column DB-5MS showed the best separation and retention properties of the targeted cannabinoids among the tested GC column phases. Also, characteristic fragment ions were observed in each electron ionization-mass spectrum. The observed fragment ions were mainly derived from α-cleavage of ketone and α-cleavage of amine for AAIs, simple cleavage for CPs, and McLafferty rearrangements for HU-210.   Based on the ionization efficiency of the target analytes using LC/MS/MS, electrospray ionization positive mode was selected for AAIs, and negative mode for CPs and HU-210. All analytes were completely separated by gradient elution of ammonium formate aqueous solution-acetonitrile mobile phase on a C18 (ODS) separation column. In addition, characteristic fragment ions were observed in product ion spectra of AAIs and second generation product ion spectra of CPs and HU-210, enabling reliable confirmation.   These results provide useful information not only for simultaneous analyses of the targeted cannabinoids but also for structural assignment of future cannabimimetic compounds that may appear in the illicit drug market.

著者

松田 駿太朗 片木 宗弘 西岡 裕 鎌田 寛恵 佐々木 啓子 志摩 典明 鎌田 徹 三木 昭宏 辰野 道昭 財津 桂 坪井 健人 土橋 均 鈴木 廣一

出版者

日本法科学技術学会

雑誌

日本法科学技術学会誌 (ISSN:18801323)

巻号頁・発行日

vol.19, no.2, pp.77-89, 2014 (Released:2014-07-30)

参考文献数

12

被引用文献数

12 19

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Cathinone-type designer drugs are a newly-encountered drug family that has a β-ketophenethylamine skeleton. Recently, the abuse of these drugs has been increasingly common among young adults, and this has caused a serious social problem in many countries. Many of those drugs have become regulated by the Pharmaceutical Affairs Act, and some of them were later banned by the Narcotics and Psychotropics Control Act in Japan, depending on their structures. In this paper, a total of 98 standards of cathinone-type designer drugs were synthesized, and their EI-mass spectra were acquired by GC/MS, with and without trifluoroacetylation. For their free bases, a major fragment ion formed from the α-cleavage of the amine nitrogen was commonly observed. Also, a small fragment ion generated by the α-cleavage of the carbonyl group, followed by the elimination of CO was detectable. For the analogs having an N-alkyl chain longer than methyl group and/or the alkyl side-chain longer than methyl group, a characteristic ion formed from the α-cleavage of the amine nitrogen, followed by the elimination of the olefin moiety was observed. For the trifluoroacetyl derivatives, the intensity of fragment ion formed from the α-cleavage of carbonyl group significantly increased, while that of the fragment ion generated from the α-cleavage of nitrogen decreased, when compared with those of free bases. Also, the ion at m/z 110 was specifically observed for the cathinone analogs having a methylamino group. Those typical fragmentation patterns revealed by analyzing a series of analogs provide useful information for the characterization of cathinone-type designer drugs.

著者

片木 宗弘 辰野 道昭 土橋 均

出版者

公益社団法人 日本薬学会

雑誌

衛生化学 (ISSN:0013273X)

巻号頁・発行日

vol.40, no.4, pp.357-364, 1994-08-31 (Released:2008-05-30)

参考文献数

20

被引用文献数

4 4

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The procedure for the determination of the main metabolites of malathion (MA), malaoxon (MO), malathion dicarboxylic acid (DCA), malathion α-, β-monocarboxylic acid (α-, β-MCA), desmethyl malathion (DM-MA), in addition to unchanged MA was investigated using positive-ion mode thermospray liquid chromatography-mass spectrometry (TSP-LC/MS). Following the solid-phase extraction of the sample at pH 2 using Sep-Pak C18 cartridge with methanol as eluent, the extract was analyzed on TSP-LC/MS. LC analyses were performed on C18-bonded phase using methanol-100 mM ammonium acetate (60 : 40 v/v, pH 3.65 with trifluoro acetic acid) as eluent at a flow rate of 1.0 ml/min. Every mass spectrum of MA and its metabolites provided both the protonated molecular ion [M+H]+ and the ammonium adduct ion [M+NH4]+. By the solid-phase extraction, they were recovered relatively well, and the detection limits were ranged from 0.2 μg/ml to 2.5 μg/ml by scan mode, ranged from 5 ng/ml to 200 ng/ml by selected ion monitering (SIM) mode. In the urine sample, the coefficients of variations for the prepared method by SIM mode were ranged from 3.3% to 7.2% at 500 ng/ml level of each metabolite. For a blood sample of a female, who had committed suicide by taking MA, TSP-LC/MS analysis were attemped following the prepared method, the metabolites such as α-MCA were detected, and it was possible to prove that she had taken MA.